EP0397003B1 - Masse à mouler thermoplastique - Google Patents

Masse à mouler thermoplastique Download PDF

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Publication number
EP0397003B1
EP0397003B1 EP90108207A EP90108207A EP0397003B1 EP 0397003 B1 EP0397003 B1 EP 0397003B1 EP 90108207 A EP90108207 A EP 90108207A EP 90108207 A EP90108207 A EP 90108207A EP 0397003 B1 EP0397003 B1 EP 0397003B1
Authority
EP
European Patent Office
Prior art keywords
weight
graft
rubber
impact
polystyrene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP90108207A
Other languages
German (de)
English (en)
Other versions
EP0397003A1 (fr
Inventor
Uwe Dr. Blumenstein
Adolf Dr.Prof. Echte
Peter Dr. Klaerner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0397003A1 publication Critical patent/EP0397003A1/fr
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Publication of EP0397003B1 publication Critical patent/EP0397003B1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers

Definitions

  • the invention relates to an improved molding composition based on impact-modified polystyrene.
  • (1) describes the extrusion of impact-resistant polystyrene with an emulsion graft rubber which has a polybutadiene core and a polystyrene graft shell.
  • the impact strength of the product is superior to both the impact-resistant polystyrene used and a polystyrene that is tough-modified only with the emulsion graft rubber.
  • a molding compound made from a matrix of polystyrene or — preferably — impact-modified polystyrene and rubber embedded in the form of discrete particles;
  • the molding compound is predominant, i.e. at least 50% by weight of polystyrene A and also from an effective amount of e.g. at least 10 to 50% by weight of a graft rubber B.
  • this consists of 40 to 95% by weight of a rubber-elastic graft core b 1 and 5 to 60% by weight of a graft cover b 2;
  • the graft cover b2 is in turn and constructed according to the invention from a first graft cover b21, which makes up 5 to 50% by weight of the total graft cover b2 and consists of styrene and 50 to 95% by weight of a second graft cover b22.
  • the second graft shell b22 is now composed of 60 to 90 wt .-% styrene b221) and 10 to 40 wt .-% acrylonitrile b222), where A and B, b1 and b2, b21 and b22 as well as b221 and b222 each 100 Add% by weight.
  • the molding composition according to the invention preferably has the following composition: 60 to 90 wt% A; 10 to 40 wt% B; 50 to 90 wt% b1; 10 to 50 wt% b2; 7 to 40 wt% b21; 60 to 93 wt .-% b22 65 to 85 wt .-% b221 15 to 35 wt .-% b222.
  • it can contain customary auxiliaries and additives and can be combined with suitable or compatible other polymers, e.g. be mixed with polyphenylene ether in all proportions. Such blends sometimes show particularly advantageous properties.
  • the combination of properties mentioned makes the molding composition according to the invention e.g. especially suitable for the refrigeration area.
  • Component A is a customary, in particular an impact modified polystyrene with a rubber content of 3 to 25% by weight, which is obtained by polymerizing styrene, preferably in the presence of a rubber.
  • minor amounts for example up to 20% by weight of styrene which is alkylated in the core or in the side chain, can also be used in minor amounts.
  • a natural or synthetic rubber used for the impact modification of styrene polymers is used as the rubber.
  • Suitable rubbers for the purposes of the invention, in addition to natural rubber, are e.g. Polybutadiene, polyisoprene, copolymers of butadiene and / or isoprene with styrene and other comonomers or acrylate rubber, which have a glass transition temperature below -20 ° C.
  • Suitable impact-resistant polystyrenes are commercially available, the mean particle size (d50 value of the integral mass distribution) in the range from 0.2 to 7 ⁇ m with a VZ of the hard matrix of 50 to 100 ml / g (0.5% in toluene at 23 ° C).
  • Component B has the features essential to the invention. It is an emulsion graft polymer whose rubber-elastic graft core can be a rubber which is customary for the impact modification of styrene polymers, as described above under component A.
  • the elastomer, the graft b1 is prepared by polymerizing butadiene or n-butyl acrylate alone, optionally together with the other comonomers in an aqueous emulsion in a known manner at a temperature of 20 to 100, preferably from 50 to 80 ° C.
  • Usual emulsifiers such as alkali salts of alkyl or alkylarylsulfonic acids, alkyl sulfites, fatty alcohol sulfonates, salts of higher fatty acids with 10 to 30 carbon atoms or resin soaps can be used.
  • the sodium salts of alkyl sulfonates or fatty acids having 10 to 18 carbon atoms are preferably used.
  • the emulsifier in an amount of 0.5 to 5% by weight, in particular 0.5 to 2% by weight, based on the monomers used in the preparation of the graft base b 1.
  • a water / monomer ratio of 2: 1 to 0.7: 1 is used.
  • the usual persulfates, such as potassium persulfate, are used in particular as polymerization initiators, but redox systems can also be used.
  • the initiator is generally used in an amount of 0.1 to 1 wt .-%, based on the monomers used in the preparation of the graft base a1.
  • buffer substances by means of which pH values are preferably set from 6 to 9, for example sodium bicarbonate and sodium, can be used as further polymerization auxiliaries serve pyrophosphate; Furthermore, 0.1 to 3% by weight of a molecular weight regulator, such as mercaptans, terpinols or dimeric ⁇ -methylstyrene, are generally used in the polymerization.
  • a molecular weight regulator such as mercaptans, terpinols or dimeric ⁇ -methylstyrene
  • the exact polymerization conditions in particular the type, dosage and amount of the emulsifier, are chosen within the above ranges in such a way that the latex of the polymer b1 obtained has a d30 value in the range from about 75 to 750 nm, preferably in the range from 100 to 700 nm. Or else the emulsion polymer with average particle sizes in the range from 60 to 150 nm is agglomerated in a known manner (cf. DE-AS 24 27 960).
  • the graft shell, component b2 has a two-stage structure and is produced by successive polymerization of the monomers b21 and b22 in 2 process steps in the presence of the latex of the elastomer b1.
  • styrene is first used in the first process stage. The person skilled in the art knows how to achieve this goal (presentation of the monomers, addition during the polymerization and the like).
  • the graft copolymerization can advantageously be carried out in the same system as the emulsion polymerization for the preparation of the graft base b 1, wherein, if necessary, further emulsifier and initiator can be added.
  • the monomer to be grafted on can be added to the reaction mixture all at once, batchwise in several stages or, preferably, continuously during the polymerization.
  • the graft copolymerization in the presence of the elastomer is carried out so that the elastomeric core has a share of 40 to 95%, preferably 50 to 90%, of the emulsion graft rubber. Accordingly, the total graft cover b2 has a share of 5 to 60%, preferably 10 to 50%.
  • the first graft cover b21 has a share of 5 to 50% of the total graft cover b2, preferably 7 to 40%.
  • the graft polymerization is then carried out with a monomer mixture of styrene, b221 and acrylonitrile, b222.
  • the second step of the graft copolymerization is also advantageously carried out in the same system; if necessary, further emulsifier and initiator can be added.
  • the monomer mixture to be grafted on i.e. the mixture of styrene and acrylonitrile can be added to the reaction mixture all at once, batchwise in several stages or, preferably, continuously during the polymerization.
  • the graft copolymerization of the mixture of styrene and acrylonitrile in the presence of the reaction product from the 1st graft stage is carried out in such a way that the proportion of the 2nd graft shell b22 in the total graft shell is 50 to 95%, preferably 60 to 93%, and the ratio of b221 to b222 ranges from 60 to 40 to 90 to 10, preferably 65 to 35 to 85 to 15 results.
  • the graft copolymers should have average particle sizes of 75 to 750 nm. Suitable graft copolymerization conditions to obtain particle sizes in this range are known and e.g. in DE-PS 12 60 135 and DE-OS 28 28 925 and in Journal of Applied Polymer Science, Vol. 9 (1965), pp. 2929 to 2938.
  • the rubber B also contains a smaller proportion of a non-elastomeric hard component which is a by-product of the graft copolymerization and consists of free, non-grafted copolymers or homopolymers of the graft monomers.
  • a non-elastomeric hard component which is a by-product of the graft copolymerization and consists of free, non-grafted copolymers or homopolymers of the graft monomers.
  • these products are classified as component B.
  • mixtures according to the invention are compared with commercial polystyrene grades not according to the invention or with the underlying impact-modified polystyrene varieties.
  • Emulsion rubbers B are Emulsion rubbers B
  • this example shows the superiority of B1 (S / SAN-grafted) over acrylate-grafted emulsion rubbers (B2 and B3) in the application-oriented, multiaxial puncture test on molded round disks. It is known that this test shows very sensitive intolerances.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)

Claims (2)

  1. Masse à mouler, se composant d'une matrice de polystyrène modifié dans le sens de la résistance au choc et de caoutchouc inclus sous forme de particules discrètes, contenant
    (A) au moins 50% en poids de polystyrène A et
    (B) une quantité efficace, pouvant aller jusqu'à 50% en poids, d'un caoutchouc greffé B composé de
    (b₁) 40 à 95% en poids d'un noyau de greffage b₁ ayant l'élasticité du caoutchouc et de
    (b₂) 5 à 60% en poids d'une enveloppe de greffage b₂, à savoir
    (b₂₁) 5 à 50% en poids d'une première enveloppe de greffage b₂₁ en styrène et
    (b₂₂) 50 à 95% en poids d'une seconde enveloppe de greffage b₂₂ constituée par
    (b₂₂₁) 60 à 90% en poids de styrène b₂₂₁ et
    (b₂₂₂) 10 à 40% en poids d'acrylonitrile b₂₂₂,
    chacune des sommes A et B, b₁ et b₂, b₂₁ et b₂₂ ainsi que b₂₂₁ et b₂₂₂ étant égale à 100% en poids.
  2. Masse à mouler selon la revendication 1, caractérisée par la composition suivante:
    60 à 90% en poids de A;
    10 à 40% en poids de B;
    50 à 90% en poids de b₁;
    10 à 50% en poids de b₂;
    7 à 40% en poids de b₂₁;
    60 à 93% en poids de b₂₂;
    65 à 85% en poids de b₂₂₁;
    15 à 35% en poids de b₂₂₂.
EP90108207A 1989-05-11 1990-04-30 Masse à mouler thermoplastique Expired - Lifetime EP0397003B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3915363 1989-05-11
DE3915363A DE3915363A1 (de) 1989-05-11 1989-05-11 Thermoplastische formmasse

Publications (2)

Publication Number Publication Date
EP0397003A1 EP0397003A1 (fr) 1990-11-14
EP0397003B1 true EP0397003B1 (fr) 1993-08-25

Family

ID=6380433

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90108207A Expired - Lifetime EP0397003B1 (fr) 1989-05-11 1990-04-30 Masse à mouler thermoplastique

Country Status (6)

Country Link
US (1) US5104936A (fr)
EP (1) EP0397003B1 (fr)
JP (1) JPH037754A (fr)
KR (1) KR900018250A (fr)
DE (2) DE3915363A1 (fr)
ES (1) ES2058664T3 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5492966A (en) * 1992-04-03 1996-02-20 General Electric Company Impact modified resin compositions containing lobed graft copolymers and process for the making thereof
US5486407A (en) * 1993-06-08 1996-01-23 General Electric Co. High rubber backing multi-layer ABS system which exhibits improved chemical resistance to HCFC blowing agents
JP4629266B2 (ja) * 2001-05-30 2011-02-09 株式会社岡村製作所 椅子における背凭れ構造
DE102005041402A1 (de) * 2005-09-01 2007-03-08 Röhm Gmbh Formkörper mit Lichtstreueigenschaften

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3509237A (en) * 1966-03-21 1970-04-28 Monsanto Co Abs graft polyblends containing two graft polymers having different particle sizes
DE1273180B (de) * 1966-11-12 1968-07-18 Basf Ag Thermoplastische Formmassen
US4214056A (en) * 1978-05-19 1980-07-22 Monsanto Company Method for preparing a monoalkenyl aromatic polyblend having a dispersed rubber phase as particles with a bimodal particle size distribution
GR69867B (fr) * 1979-11-20 1982-07-20 Basf Ag
US4366289A (en) * 1981-04-20 1982-12-28 The Dow Chemical Company Acrylate-grafted elastomers as polymer modifiers
DE3149358A1 (de) * 1981-12-12 1983-06-16 Basf Ag, 6700 Ludwigshafen Thermoplastische formmasse
EP0081761B1 (fr) * 1981-12-12 1985-03-27 BASF Aktiengesellschaft Masse de moulage thermoplastique

Also Published As

Publication number Publication date
ES2058664T3 (es) 1994-11-01
DE3915363A1 (de) 1990-11-15
US5104936A (en) 1992-04-14
DE59002428D1 (de) 1993-09-30
KR900018250A (ko) 1990-12-20
EP0397003A1 (fr) 1990-11-14
JPH037754A (ja) 1991-01-14

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